US4857501A - Manufacturing method of a heat sensitive recording material - Google Patents
Manufacturing method of a heat sensitive recording material Download PDFInfo
- Publication number
- US4857501A US4857501A US07/138,163 US13816387A US4857501A US 4857501 A US4857501 A US 4857501A US 13816387 A US13816387 A US 13816387A US 4857501 A US4857501 A US 4857501A
- Authority
- US
- United States
- Prior art keywords
- heat sensitive
- sensitive layer
- sensitive recording
- support
- transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
- Y10T428/24868—Translucent outer layer
- Y10T428/24876—Intermediate layer contains particulate material [e.g., pigment, etc.]
Definitions
- the present invention relates to a heat sensitive recording material, and more particularly, to a manufacturing method of a heat sensitive recording material having excellent transparency and being convenient for a special use.
- a heat-sensitive recording method has many advantages in that no particular developing step is required, (2) if paper is used as a support, the recording material can have a quality akin to that of plain paper, (3) handling of the recording material used is easy, (4) the images recorded have high color density, (5) this method can be effected using a simple and cheap apparatus and (6) no noise is caused during recording. Therefore, heat-sensitive recording materials have recently enjoyed a markedly increasing demand, particularly for use with a facsimile or printer, and have come to be used for many purposes such as a pass, a label or a score card. Moreover, it has been desired to devise transparent heat-sensitive recording materials which enable direct recording with a thermal head in order to adapt them for multicolor development, or to make them usable for an overhead projector (hereinafter abbreviated as OHP).
- OHP overhead projector
- a possibility of provision of such transparent heat-sensitive recording materials depends on a possibility of provision of a transparent heat sensitive layer, and it is easily estimated that a demand for heat-sensitive recording material will be enlarged if said transparent heat-sensitive recording material is really provided.
- a heat sensitive recording material is used for before mentioned label etc.
- a stain which is caused by unexpected coloring is occurred when an organic solvent etc. are adsorbed on the heat sensitive layer. Therefore, a protective layer comprised of a material which is not damaged by the organic solvent should be provided on the heat sensitive layer to prevent above mentioned stain.
- water such as rain often adsorbs then water soluble printing ink can not be used.
- a transparent heat sensitive recording material which is known so far can not answer to the above mentioned new needs, since the transparent heat sensitive recording material is a type which is used by contacting with original document then exposing the recording material to light; a temperature of an image part is increased by an absorption of infrared light by image part of original then the recording material is colored imagewisely.
- a transparent heat sensitive layer can be obtained by coating a mixed solution of a solution containing the microcapsules and developer dispersed solution. It has also been found that a transparency of the heat sensitive layer can be adjusted by selecting a ratio of two refractive indexes; one refractive index is that of a component contained in the microcapsule and the other is that of oily component contained in the developer emulsion.
- the first object of the present invention is to provide a method to produce a transparent heat sensitive material having a transparent heat sensitive layer.
- the second object of the present invention is to provide a method to control a transparency of a transparent heat sensitive layer.
- the third object of the present invention is to provide a heat sensitive recording material comprising a transparent heat sensitive layer provided on a printed support so that one can see the printed matter.
- the fourth object of the present invention is to provide a heat sensitive recording label comprising a transparent heat sensitive layer provided on a support on which desired matters are already printed.
- compositions containing an emulsified dispersion prepared by dispersing color developer dissolved into an organic solvent slightly soluble or insoluble in water and microcapsules containing at least a colorless or light colored electron donating dye precursor; adjusting a refractive index of a core material contained in the microcapsule and that of a nonvolatile oily phase of a dispersion comprising developer and organic solvent.
- an excellent label, pass etc. can be obtained easily by providing the transparent heat sensitive layer on a printed support.
- FIG. 1 is a conceptional cross section of an embodiment of the heat sensitive recording material of the present invention.
- symbols 1, 2 and 3 represent a support, printed image and a transparent heat sensitive layer respectively.
- Electron donating dye precursors to be employed in the present invention are selected properly from known colorless or light colored compounds of the kind which can develop their colors by donating an electron or accepting a proton of an acid or the like. These compounds have such a skeleton as that of lactone, lactam, sultone, spiropyran, ester, amide, etc., as a part of their structures, and these skeletons undergo ring-opening or bond cleavage upon contact with a color developer.
- Preferred examples of such compounds include triarylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds and so on.
- R 1 represents an alkyl group containing 1 to 8 carbon atoms
- R 2 represents an alkyl or alkoxyalkyl group containing 4 to 18 carbon atoms, or a tetrahydrofuryl group
- R 3 represents a hydrogen atom, an alkyl group containing 1 to 15 carbon atoms, or a halogen atom
- R 4 represents a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms.
- substituent group for R 4 alkyl, alkoxy and halogenated alkyl groups containing 1 to 5 carbon atoms, and halogen atoms are preferred.
- Microencapsulation of the above-described color former in the present invention can prevent generation of fog during production of a heat sensitive material and, at the same time, can improve a freshness keeping quality of a heat sensitive material and a keeping quality of the record formed.
- the image density at the time of recording can be heightened by properly selecting a material and a method for forming a microcapsule wall.
- a preferred amount of the color former used is 0.05 to 5.0 g per square meter.
- Suitable examples of wall materials for microcapsules include polyurethane, polyurea, polyester, polycarbonate, urea/formaldehyde resin, melamine resin, polystyrene, styrene/ m ethacrylate copolymer, styrene/acrylate copolymer, gelatin, polyvinyl pyrrolidone, polyvinyl alcohol, and so on. These macromolecular substances can be used in combination of two or more thereof in the present invention.
- polyurethane, polyurea, polyamide, polyester, and polycarbonate are preferred in the present invention.
- polyurethane and polyurea can bring about good results.
- Microcapsules to be employed in the present invention are preferably prepared by emulsifying a core material containing a reactive substance like a color former, and then forming a wall of a macromolecular substance around the droplets of the core material to microencapsulate the core material. Therein, reactants to produce a macromolecular substance are added to the inside and/or the outside of the oily droplets.
- a reactive substance like a color former
- reactants to produce a macromolecular substance are added to the inside and/or the outside of the oily droplets.
- An organic solvent to constitute the above-described oil droplets can be properly selected from those used generally for pressure sensitive material.
- Some of desirable oils are compounds represented by the following general formulae (I) to (III), triarylmethanes (such as tritoluylmethane, toluyldiphenylmethane), terphenyl compounds (such as terphenyl), alkylated diphenyl ethers (such as propyldiphenyl ether), hydrogenated terphenyl compounds (such as hexahydroterphenyl), diphenyl ethers, chlorinated paraffins and so on.
- triarylmethanes such as tritoluylmethane, toluyldiphenylmethane
- terphenyl compounds such as terphenyl
- alkylated diphenyl ethers such as propyldiphenyl ether
- hydrogenated terphenyl compounds such as hexahydroterphenyl
- diphenyl ethers chlorinated paraffins and so on.
- R 1 represents a hydrogen atom, or an alkyl group containing 1 to 18 carbon atoms
- R 2 represents an alkyl group containing 1 to 18 carbon atoms
- p 1 and q 1 each represents an integer of 1 to 4, provided that the total number of alkyl groups therein is 4 or less.
- Preferred alkyl groups represented by R 1 and R 2 are those containing 1 to 8 carbon atoms.
- R 3 represents a hydrogen atom, or an alkyl group containing 1 to 12 carbon atoms
- R 4 represents an alkyl group containing 1 to 12 carbon atoms
- n is 1 or 2.
- R 5 and R 6 which may be the same or different, each represents a hydrogen atom, or an alkyl group containing 1 to 18 carbon atoms.
- m represents an integer of 1 to 13.
- p 3 and q 3 each represents an integer of 1 to 3, provided that the total number of alkyl groups is 3 or less.
- alkyl groups represented by R 5 and R 6 those containing 2 to 4 carbon atoms are particularly preferred.
- Specific examples of the compounds represented by the formula (I) include dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, and the like.
- Specific examples of the compounds represented by the formula (II) include dimethylbiphenyl, diethylbiphenyl, diisopropylbiphenyl, diisobutylbiphenyl, and the like.
- Specific examples of the compounds represented by the formula (III)in include 1-methyl-1-dimethylphenyl-1-phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane, and the like.
- oils can be used as a mixture of two or more thereof, or in combination with other oils.
- a preferred size of microcapsules to be employed in the present invention is 4 microns or less, particularly 2, 5 micron or less, on a volume average basis according to the evaluation method described, e.g., in Japanese Patent Application (OPI) No. 214990/85.
- Desirable microcapsules which are produced in the above-described manner are not those of the kind which are disrupted by heat or pressure, but those of the kind which have a microcapsule wall through which reactive substances present inside and outside the individual microcapsules respectively can permeate at high temperature to react with each other.
- Multicolored neutral tints can be effected by preparing some kinds of microcapsules having walls differing in glass transition point through proper selection of wall materials, and optional addition of glass transition point controlling agents (e.g., plasticizers described in Japanese Patent Application (OPI)No. 277490/86) to the wall materials, respectively, and further by combining selectively colorless electron donating dye precursors differing in hue with their respective color developers. Therefore, the present invention is not limited to a monochromatic heat sensitive recording material but can be applied to a two-color or multicolor heat sensitive recording material and a heat sensitive recording material suitable for recording of graded image.
- glass transition point controlling agents e.g., plasticizers described in Japanese Patent Application (OPI)No. 277490/86
- OPI Japanese Patent Application
- the present invention is not limited to a monochromatic heat sensitive recording material but can be applied to a two-color or multicolor heat sensitive recording material and a heat sensitive recording material suitable for recording of graded image.
- a photodiscoloration inhibitor as described e.g., in Japanese Patent Application (OPI) Nos. 283589/86, 283590/86 and 283591/86 can be added, if desired.
- Color developers to be employed in the present invention which undergo the color development reaction with electron donating colorless precursors when heated, can be those selected properly from known color developers.
- suitable examples of color developers to be combined with leuco dyes include phenol compounds, sulfur-contained phenolic compounds, carboxylic acid compounds, sulfon compounds, urea or thiourea compounds, and so on. Details of the color developers are described, e.g., in "Kami Pulp Gijutsu Times," pp. 49-54, and pp. 65-70 (1985).
- those having melting points of 50° to 250° C., particularly phenols and organic acids which have melting points of 60° to 200° C. and are hardly soluble in water are preferred over others. Combined use of two or more of color developers is desirable because of increase in solubility.
- R 7 is an alkyl group, an aryl group, an aryloxy group, or an aralkyl group. In particular, methyl group, ethyl group and butyl group are preferred as R 7 .
- R 8 is an alkyl group. In particular, butyl group, pentyl group, heptyl group, and octyl group are preferred as R 8 .
- R 9 is a hydrogen atom or methyl group and n is 0-2.
- R 10 is an alkyl group, an aryloxy group, or an aralkyl group.
- such a color developer is used in a form of emulsified dispersion.
- the dispersion can be prepared by dissolving color developers in an organic solvent slightly soluble or insoluble in water, and mixing the resulting solution with an aqueous phase which contains a surface active agent, and a water-soluble high polymer as a protective colloid to emulsify and to disperse the solution in the aqueous phase.
- An organic solvent to be used for dissolving the color developers can be properly selected from known oils.
- esters having high boiling point or before mentioned oils used for pressure sensitive materials are preferable.
- esters are more preferable from a view point of a stability of the color developer emulsion.
- esters include phosphates (e.g.,triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl-bi-phenyl phosphate), phthalates (e.g., dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, octyl phthalate, buthlbenzyl phthalate, tetrahydro dioctyl phthalate, benzoates (e.g., ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate), abietates(e.g., ethyl abietate, benzyl abietate ), dioctyl adipate, diethyl succinate, isodecyl succinate, dioctyl adip
- Organic solvents having boiling point lower than 150° C. can be added to the foregoing organic solvents. Some of these organic solvents are ethylacetate, isopropyl acetate, butyl acetate, methylene chloride, and the like.
- Water soluble high polymers to be contained as a protective colloid in an aqueous phase, which is to be mixed with an oily phase wherein color developers are dissolved can be selected properly from known anionic, nonionic or amphoteric high polymers.
- these high polymers polyvinylalcohol, gelatin, cellulose derivatives and the like are preferred.
- Surface active agents to be contained additionally in the aqueous phase can be selected properly from anionic or nonionic surface active agents of the kind which do not cause any precipitation or condensation by interaction with the above-described protective colloids.
- surface active agents which can be preferably used, mention may be made of sodium alkylbenzenesulfonates (such as sodium laurylbenzenesulfonate ), sodium dioctylsulfosuccinates, polyalkylene glycols (such as polyoxyethylene nonylphenyl, ether) and so on.
- An emulsified dispersion of color developers to be used in the present invention can be prepared with ease by mixing an oil phase containing the color developers and an aqueous phase containing a protective colloid and a surface active agent with a general means for preparing a fine grain emulsion, such as a high-speed stirrer, an ultrasonic disperser or so on, to disperse the former phase into the latter phase.
- a general means for preparing a fine grain emulsion such as a high-speed stirrer, an ultrasonic disperser or so on, to disperse the former phase into the latter phase.
- melting point depressants for the color developers can be added, if desired.
- Some of these melting point depressants have such a function as to control glass transition points of the capsule walls described hereinbefore, too.
- Specific examples of such melting point depressants include hydroxy compounds, carbamate compounds, sulfonamide compounds, aromatic methoxy compounds and so on. Details of these compounds are described in Japanese Patent Application No. 244190/84.
- melting point depressants can be used in an amount of 0.1 to 2 parts by weight, preferably 0.5 to 1 part by weight, per 1 part by weight of color developer whose melting point is to be depressed. It is to be desired that the melting point depressant and the color developer, whose melting point can be depressed thereby, should be used in the same place. When they are added to separate places, a preferred addition amount of the melting point depressant is 1 to 3 times of that of the above-described one.
- the heat sensitive recording material of the present invention is produced by providing a heat sensitive layer on a support, such as paper, a synthetic resin film, etc., coating and drying a coating composition, in which microcapsules enclosing a color former therein and a dispersion containing at least a color developer in an emulsified condition are contained as main components, and further a binder and other additives are incorporated, according to a conventional coating method, such as a bar coating method, a blade coating method, an air knife coating method, a gravure coating method, a roll coating method, a spray coating method, a dip coating method, or so on.
- a coverage of the heat sensitive layer is controlled to 2.5 to 25 g/m 2 on a solid basis.
- the transparency can be estimated by measuring Haze (%) using HTR meter (integrating - sphere photometer) manufactured by Nippon Seimitsu Kogyo K.K.
- HTR meter integrating - sphere photometer
- a transparent adhesive tape is stuck on the surface of the heat sensitive layer to prevent the light scattering then measurement is carried out to estimate an intrinsic transparency of the heat sensitive layer.
- haze % of the heat sensitive layer can be reduced to less than 30% when the refractive index of the former is 0.97-1.03 times of that of the latter. Especially, haze % can be reduced to less than 20% by making said ratio into a range of 0.99-1.01.
- the transparency of the heat sensitive layer can easily be controlled by adjusting the refractive index of the component contained in the microcapsule (core material) and that of aforementioned oil phase in the emulsified dispersion.
- pigments such as silica, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, calcium carbonate, etc., styrene beads, or fine particles of urea/melamine resin and so on can be added to the heat sensitive recording material of the present invention.
- metal soaps can be added for the purpose of prevention of the sticking phenomenon. They are used at a coverage of 0.2 to 7 g/m 2 .
- the heat sensitive recording material of the present invention can be formed using a coating technique with the aid of an appropriate binder.
- water soluble polymers and various kinds of emulsions such as a polyvinyl alcohol, a methyl cellulose, a carboxymethyl cellulose, a hydroxypropyl cellulose, a gum arabic, a gelatin, a polyvinyl pyrrolidone, a casein, a styrene-butadiene latex, an acrylonitrile-butadiene latex, a polyvinyl acetate emulsion, a polyacrylate emulsion, an ethylene-vinyl acetate copolymer emulsion, and so on, can be employed.
- An amount of the binder used is 0.2 to 5 g per square meter on a solids basis.
- polymers used in the protective layer are a methylcellulose, a carboxymethylcellulose, a hydroxymethylcellulose, a starch, a gelatin, a gum arabic, a casein, a hydrolyzed product of styrene-maleic anhydride copolymer, a hydrolyzed half-ester product of styrenemaleic anhydride copolymer, hydrolyzed product of isobutylene-maleic anhydride copolymer, a polyvinylalcohol, a modified polyvinylalcohol with silicon, a modified polyvinylalcohol with carboxyl group, a polyacrylamide derivatives, a polyvinyl pyrrolidone, a polystyrene sodium sulfate, a metal salt of alginic acid, styrene-butadiene rubber latex, acrylonitrile-butadienebutadiene rubber latex, methylacrylate-butadiene rubber
- the modified polyvinylalcohol with silicon is preferable.
- These binders can be used singly or in combination.
- a preferred amount of the latter is from 0.01 to 0.5 part by weight per 1 part by weight of modified polyvinylalcohol with silicon.
- a pigment, metal soap, wax or cross-linking agent etc. can be added in order to improve matching of the heat sensitive material with thermal head when thermal recording is performed or to improve water resisting property of the protective layer.
- pigments are a zinc oxide, a calcium carbonate, a barium sulfate, a titanium oxide, a lithopone, a talc, an agalmatolite, a kaolin, an aluminum hydroxide, an amorphous silica etc.
- an amount to be added is 0.05-2 times of an amount of total weight of polymer, especially 0.1-0.5 times are preferable.
- An amount less than 0.05 times can not improve the matching of the heat sensitive recording material with thermal head, on the other hand an amount more than 2 times reduces both transparency and sensitivity of the heat sensitive recording material remarkably, which causes damage on commercial value.
- metal soaps are an emulsion of metal salt of higher fatty acid (e.g., a zinc stearate, a calcium stearate, an aluminum stearate) etc., and its amount to be added is 0.5-20 weight %, preferably 1-10 weight % against total weight of the protective layer.
- Some of the waxes are a paraffin wax, a microcrystalline wax, a carnauba wax, a methylol stearoamide, a polyethylene wax, an emulsion of silicone etc., and an amount thereof to be added is 0.5-40 weight %, preferably 1-20 weight % against total weight of the protective layer.
- a surface active agent is added in order to prepare the protective layer uniforming on the heat sensitive layer.
- the active agents are an alkali metal salt of sulfosuccinic acid group and an active surface agent containing fluorine atoms etc., concretely they are a sodium salt or an ammonium salt etc., of a di-(2ethylhexyl) sulfosuccinic acid or di-(n-hexyl) sulfosuccinic acid etc.
- a preferable amount of the protective layer to be coated is usually 0.2-5 g/m 2 , particularly 1 g-3 g/m 2 at the solids coverage.
- an opaque base such as a paper or an undercoated paper as well as a known transparent polymer film can be used in the present invention.
- a heat sensitive recording material of the present invention is intended to use for OHP, A polyethyleneterephthalate film (PET) and cellulosetriacetate film (TAc) are preferably use as the support from a view point of dimensional stability and strength etc.
- neutralized paper which is sized with a neutral sizing agent like an alkylketene dimer and shows pH 6-9 upon hot extraction (Japanese Patent Application (OPI) No. 14281/'80) is employed to advantage in the respect of long-range preservation.
- Stokigt sizing degree/(meter basis weight) 2 ⁇ 3 ⁇ 10 - 3 and Beck smoothness of 90 seconds or more, is used to advantage.
- paper having optical surface roughness of 8 microns or less and a thickness of 40 to 75 microns as described in Japanese Patent Application (OPI) No. 136492/83; paper having a density of 0.9 g/cm 3 or less and optical contact rate of 15% or more, as described in Japanese Patent Application (OPI) No. 69097/83; paper which is prepared from pulp having received a beating treatment till its freeness has come to 400 cc or more on a basis of Canadian Standard Freeness (JIS P8121) to prevent permeation of a coating composition thereinto, as described in Japanese Patent Application (OPI) No.
- a transparency of heat sensitive recording layer of the present invention can easily be adjusted by controlling a refractive index of a component contained in a microcapsule and that of a oily phase in a color developer emulsified dispersion.
- the solution of the above-described leuco dye was mixed with an aqueous solution constituted with 100 g of a 8% water solution of polyvinyl alcohol, 40 g of water and 1.4 g of a 2% water solution of sodium dioctylsulfosuccinate (dispersant), and emulsified with stirring at 10,000 r.p.m. for 5 minutes using Ace Homogenizer made by Nippon Seiki K.K.. Then, the resulting emulsion was diluted with 150 g of water, and allowed to stand at 40° C. for 3 hours to conduct the microencapsulation reaction therein. Thus, a solution containing microcapsules having size of 0.7 micron was obtained.
- the color developers (a), (b) and (c) represented by the structural formulae illustrated below were added in amounts of 8 g, 4 g and 30 g, respectively, to a solvent mixture of 2.0 g of 1-phenyl-1-xylylethane, 6.0 g of dibutylphthalate and 30 g of ethyl acetate, and dissolved thereinto.
- the thus obtained solution of the color developers was mixed with 100 g of a 8% water solution of polyvinyl alcohol, 150 g of water and 0.5 g of sodium dodecylbenzensulfonate, and emulsified with stirring at 10,000 r.p.m. for 5 minute at ordinary temperature using Ace Homogenizer made by Nippon Seiki k.k. to prepare an emulsified dispersion having a grain size of 0.5 micron.
- Ace Homogenizer made by Nippon Seiki k.k.
- a 5.0 g portion of the foregoing capsule solution, a 10.0 g portion of the foregoing color developer-emulsified dispersion and 5.0 g of water were mixed with stirring, coated on a 70 micron-thick transparent polyethylene terephthalate (PET) film support at a coverage of 15 g/m 2 on a solids basis, and dried. Thereon, a 2 micron-thick protective layer having the following composition was further provided to produce a transparent heat sensitive film.
- PET polyethylene terephthalate
- thermal recording was carried out using a G III-mode thermal printer (Mitsubishi Melfas 600 (trade name) manufactured by Mitsubishi Denki K.K.) and blue image was obtained.
- a transmittal image density was measured as 0.7 using McBeth densitometer and the image was able to see by OHP.
- a transparent black image was obtained by the same procedure as in Example 1 except using the following oil cited in the table 1 instead of oils of the 1-phenyl-1-xylylethane and the dibutyl phthalate used for the preparation of a color developer emulsified dispersion.
- FIG. 1 is a cross section of the present heat sensitive recording material which is used for labels.
- a symbol 1 is a support
- 2 represents an image printed on the support
- 3 is the present transparent heat sensitive layer prepared in Example 1. Since the transparency of the heat sensitive layer is excellent, images printed on the support are able to see through the heat sensitive layer. This fact proves that desired matters can be printed on a support before a heat sensitive layer is coated on the support. Therebefore, papers, which are able to absorb ink easily, can be used as a support and printing on the support using a cheap aqueous ink is possible, then a blocking phenomenon can be prevented. It easily estimated that if necessary, a transparent film and the like can be used as the support.
- a 5.0 g portion of the foregoing capsule solution, a 10.0 g portion of the foregoing color developer-emulsified dispersion and 5.0 g of water were mixed with stirring, coated on a 70 micron-thick transparent polyethylene terephthalate (PET) film support at a coverage of 15 g/m 2 on a solid basis, and dried. Thereon, a 2 micron-thick protective layer having the following composition was further provided to produce a transparent heat sensitive film.
- PET polyethylene terephthalate
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61-203748 | 1986-12-25 | ||
JP20374886U JPS63104054U (fr) | 1986-12-25 | 1986-12-25 | |
JP62-088197 | 1987-04-09 | ||
JP62-088196 | 1987-04-09 | ||
JP62088197A JPH074986B2 (ja) | 1986-05-26 | 1987-04-09 | 感熱記録材料 |
JP62088196A JPH0662011B2 (ja) | 1987-04-09 | 1987-04-09 | 感熱記録材料 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4857501A true US4857501A (en) | 1989-08-15 |
Family
ID=27305763
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/138,163 Expired - Lifetime US4857501A (en) | 1986-12-25 | 1987-12-28 | Manufacturing method of a heat sensitive recording material |
Country Status (3)
Country | Link |
---|---|
US (1) | US4857501A (fr) |
EP (1) | EP0273752B1 (fr) |
DE (2) | DE3781259T2 (fr) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5198321A (en) * | 1990-10-03 | 1993-03-30 | Fuji Photo Film Co., Ltd. | Image forming method |
US5260715A (en) * | 1988-06-28 | 1993-11-09 | Fuji Photo Film Co., Ltd. | Method of and apparatus for thermally recording image on a transparent heat sensitive material |
US5665670A (en) * | 1995-08-30 | 1997-09-09 | Eastman Kodak Company | Recording element for direct thermosensitive printing |
US6127314A (en) * | 1997-08-29 | 2000-10-03 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
US20070087144A1 (en) * | 2005-10-18 | 2007-04-19 | Multi-Color Corporation | Shrink sleeve for an article closure |
US20080018098A1 (en) * | 2006-07-17 | 2008-01-24 | Ward/Kraft | Card carrying business communication product and method of producing same |
US7425296B2 (en) | 2004-12-03 | 2008-09-16 | Pressco Technology Inc. | Method and system for wavelength specific thermal irradiation and treatment |
US8303290B2 (en) | 2004-11-22 | 2012-11-06 | Sidel Participations | Method and installation for the production of containers |
US8546277B2 (en) | 2007-03-02 | 2013-10-01 | Sidel Participations | Heating plastics via infrared radiation |
US8662876B2 (en) | 2007-06-11 | 2014-03-04 | Sidel Participations | Installation for heating the bodies of preforms for blow-moulding containers |
US8932706B2 (en) | 2005-10-27 | 2015-01-13 | Multi-Color Corporation | Laminate with a heat-activatable expandable layer |
US9878567B2 (en) | 2013-11-15 | 2018-01-30 | Osaka Sealing Printing Co., Ltd. | Thermal recording sheet |
US20190022989A1 (en) * | 2016-01-14 | 2019-01-24 | Osaka Sealing Printing Co., Ltd. | Packaging sheet, and packaging container and packaging method using the packaging sheet |
US10857722B2 (en) | 2004-12-03 | 2020-12-08 | Pressco Ip Llc | Method and system for laser-based, wavelength specific infrared irradiation treatment |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06104385B2 (ja) * | 1987-12-01 | 1994-12-21 | 富士写真フイルム株式会社 | 感熱記録材料 |
EP0715964B2 (fr) * | 1994-12-09 | 2002-10-30 | Ricoh Company, Ltd | Elément d'enregistrement thermosensible |
JPH08169179A (ja) * | 1994-12-19 | 1996-07-02 | Fuji Photo Film Co Ltd | 記録材料 |
JP4137403B2 (ja) * | 2001-05-01 | 2008-08-20 | 富士フイルム株式会社 | 記録材料及び画像形成方法 |
EP3680110B1 (fr) | 2019-01-14 | 2022-11-09 | Ricoh Company, Ltd. | Matériel d'enregistrement thermosensible |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4577205A (en) * | 1984-05-25 | 1986-03-18 | Ricoh Electronics, Inc. | Releasable heat-sensitive label with E. B. setting printing ink |
US4711874A (en) * | 1984-08-20 | 1987-12-08 | Ricoh Company, Ltd. | Thermosensitive recording adhesive sheet |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2929736A (en) * | 1957-07-25 | 1960-03-22 | Ncr Co | Heat and pressure responsive record material |
JPS492126B1 (fr) * | 1970-10-27 | 1974-01-18 | ||
BE776015A (fr) * | 1970-12-28 | 1972-03-16 | Mitsui Toatsu Chemicals | Materiel d'enregistrement sensible a la pression |
JPS5016967B1 (fr) * | 1971-08-04 | 1975-06-17 | ||
DE2909950A1 (de) * | 1979-03-14 | 1980-10-02 | Bayer Ag | Mikrokapseln |
US4343652A (en) * | 1979-08-24 | 1982-08-10 | Monsanto Europe S.A. | Chromogen solutions for pressure-sensitive mark-recording systems |
JPS59218890A (ja) * | 1983-05-27 | 1984-12-10 | Mitsubishi Paper Mills Ltd | 単一層型自己発色性感圧記録紙 |
JPS60242094A (ja) * | 1984-05-17 | 1985-12-02 | Fuji Photo Film Co Ltd | 感熱記録材料 |
JPS6141593A (ja) * | 1984-08-06 | 1986-02-27 | Nippon Petrochem Co Ltd | 感圧紙染料用溶剤 |
-
1987
- 1987-12-24 DE DE8787311474T patent/DE3781259T2/de not_active Expired - Lifetime
- 1987-12-24 DE DE8787311474T patent/DE3781259D1/de not_active Expired - Fee Related
- 1987-12-24 EP EP87311474A patent/EP0273752B1/fr not_active Expired - Lifetime
- 1987-12-28 US US07/138,163 patent/US4857501A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4577205A (en) * | 1984-05-25 | 1986-03-18 | Ricoh Electronics, Inc. | Releasable heat-sensitive label with E. B. setting printing ink |
US4711874A (en) * | 1984-08-20 | 1987-12-08 | Ricoh Company, Ltd. | Thermosensitive recording adhesive sheet |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5260715A (en) * | 1988-06-28 | 1993-11-09 | Fuji Photo Film Co., Ltd. | Method of and apparatus for thermally recording image on a transparent heat sensitive material |
US5198321A (en) * | 1990-10-03 | 1993-03-30 | Fuji Photo Film Co., Ltd. | Image forming method |
US5665670A (en) * | 1995-08-30 | 1997-09-09 | Eastman Kodak Company | Recording element for direct thermosensitive printing |
US6127314A (en) * | 1997-08-29 | 2000-10-03 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
US8303290B2 (en) | 2004-11-22 | 2012-11-06 | Sidel Participations | Method and installation for the production of containers |
US8354051B2 (en) | 2004-11-22 | 2013-01-15 | Sidel Participations | Method and installation for the production of containers |
US11072094B2 (en) | 2004-12-03 | 2021-07-27 | Pressco Ip Llc | Method and system for wavelength specific thermal irradiation and treatment |
US10857722B2 (en) | 2004-12-03 | 2020-12-08 | Pressco Ip Llc | Method and system for laser-based, wavelength specific infrared irradiation treatment |
US7425296B2 (en) | 2004-12-03 | 2008-09-16 | Pressco Technology Inc. | Method and system for wavelength specific thermal irradiation and treatment |
US20110177267A9 (en) * | 2005-10-18 | 2011-07-21 | Multi-Color Corporation | Shrink sleeve for an article closure |
US20070087144A1 (en) * | 2005-10-18 | 2007-04-19 | Multi-Color Corporation | Shrink sleeve for an article closure |
US8932706B2 (en) | 2005-10-27 | 2015-01-13 | Multi-Color Corporation | Laminate with a heat-activatable expandable layer |
US7735251B2 (en) * | 2006-07-17 | 2010-06-15 | Ward/Kraft, Inc. | Card carrying business communication product and method of producing same |
US20080018098A1 (en) * | 2006-07-17 | 2008-01-24 | Ward/Kraft | Card carrying business communication product and method of producing same |
US8546277B2 (en) | 2007-03-02 | 2013-10-01 | Sidel Participations | Heating plastics via infrared radiation |
US8662876B2 (en) | 2007-06-11 | 2014-03-04 | Sidel Participations | Installation for heating the bodies of preforms for blow-moulding containers |
US9878567B2 (en) | 2013-11-15 | 2018-01-30 | Osaka Sealing Printing Co., Ltd. | Thermal recording sheet |
US20190022989A1 (en) * | 2016-01-14 | 2019-01-24 | Osaka Sealing Printing Co., Ltd. | Packaging sheet, and packaging container and packaging method using the packaging sheet |
US10882290B2 (en) * | 2016-01-14 | 2021-01-05 | Osaka Sealing Printing Co., Ltd. | Packaging sheet, and packaging container and packaging method using the packaging sheet |
Also Published As
Publication number | Publication date |
---|---|
DE3781259D1 (de) | 1992-09-24 |
EP0273752B1 (fr) | 1992-08-19 |
EP0273752A2 (fr) | 1988-07-06 |
DE3781259T2 (de) | 1993-03-11 |
EP0273752A3 (en) | 1989-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4820682A (en) | Heat sensitive recording materials | |
US4840933A (en) | Heat sensitive recording material | |
US4857501A (en) | Manufacturing method of a heat sensitive recording material | |
US4999333A (en) | Heat sensitive recording material | |
US4929411A (en) | Heat-sensitive recording material | |
US6613716B2 (en) | Thermal print paper and process | |
JPS61244587A (ja) | 感熱記録材料 | |
US4845071A (en) | Heatsensitive recording material | |
JPH09263047A (ja) | 感熱記録体 | |
JP2514068B2 (ja) | 感熱記録材料 | |
JPH0825335B2 (ja) | 感熱記録材料 | |
JPS6186283A (ja) | 感熱記録材料 | |
US5593938A (en) | Thermal-sensitive recording material | |
JPH0745261B2 (ja) | 感熱記録材料 | |
JPH0662011B2 (ja) | 感熱記録材料 | |
JPH04325285A (ja) | 感熱記録材料 | |
JPH0698836B2 (ja) | 感熱記録材料 | |
JPS63189286A (ja) | 感熱記録材料 | |
JPH085248B2 (ja) | 感熱記録材料 | |
JPH01105780A (ja) | 感熱記録材料 | |
JPS61283590A (ja) | 感熱記録材料 | |
JPH01263079A (ja) | 感熱記録材料 | |
JPH0739218B2 (ja) | 感熱記録材料 | |
JPH01204785A (ja) | 感熱記録材料 | |
JPS6241082A (ja) | 感熱記録材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: FUJI PHOTO FILM CO., LTD., 210, NAKANUMA, MINAMIAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:USAMI, TOSHIMASA;SHIMOMURA, AKIHIRO;TATSUTA, SUMITAKA;AND OTHERS;REEL/FRAME:004997/0583 Effective date: 19871211 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FEPP | Fee payment procedure |
Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
REFU | Refund |
Free format text: REFUND OF EXCESS PAYMENTS PROCESSED (ORIGINAL EVENT CODE: R169); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FEPP | Fee payment procedure |
Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: FUJIFILM CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FUJIFILM HOLDINGS CORPORATION (FORMERLY FUJI PHOTO FILM CO., LTD.);REEL/FRAME:020817/0190 Effective date: 20080225 Owner name: FUJIFILM CORPORATION,JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FUJIFILM HOLDINGS CORPORATION (FORMERLY FUJI PHOTO FILM CO., LTD.);REEL/FRAME:020817/0190 Effective date: 20080225 |